CN112028872B - Synthetic method of dibenzoselenophene compound - Google Patents

Synthetic method of dibenzoselenophene compound Download PDF

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CN112028872B
CN112028872B CN202010976857.2A CN202010976857A CN112028872B CN 112028872 B CN112028872 B CN 112028872B CN 202010976857 A CN202010976857 A CN 202010976857A CN 112028872 B CN112028872 B CN 112028872B
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周云兵
李金承
刘妙昌
吴华悦
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Wenzhou University
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Abstract

The invention discloses a synthetic method for preparing a dibenzoselenophene compound. The method is characterized in that a C-Se bond is formed through the free radical cyclization of a biaryl boric acid substrate catalyzed by TMSCN and selenium powder, so that a dibenzoselenophene compound is constructed. The new strategy has the advantages of no metal participation, no additive promotion, wide substrate range, good functional group compatibility, simple operation, high yield and the like.

Description

Synthetic method of dibenzoselenophene compound
Technical Field
The application belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of a dibenzoselenophene compound.
Background
Selenophene derivatives have attracted much attention in fields such as organic synthetic chemistry, material science, organic optoelectronic devices, etc., and particularly have exhibited good properties in the field of optoelectronic devices, and have become a new research hotspot in the field of optoelectronic materials. However, in the research on the preparation of selenophen derivatives, due to the difficulty in the source of selenophen as the starting material and the harsh conditions of the preparation process, the chemical development of selenophen is relatively slow, and the rapid development of selenophen chemistry is greatly influenced (the progress of the research on the preparation and application of selenophen derivatives, Lichuli, etc., book of university of Henan (Nature science edition), Vol.43, No. 3, No. 258, page 264, and No. 5 months of 2013).
Dibenzoselenophene compounds are common basic skeleton structural units in selenophene derivatives and widely appear in material molecules. The method for preparing the dibenzoselenophene compound in the prior art mainly comprises (1) constructing a complex and expensive catalytic reaction system by using a diaryl selenoether compound as a raw material and using noble metals Pd, Ag and the like and/or transition metals Cu, Ti, Mo and the like as catalysts to prepare and obtain the dibenzoselenophene compound (see ACS Catalysis,10(4), 2707-; (2) aryl diselenide compounds are used as raw materials in the presence of metal catalysts such as Mo, Pd and the like and/or halogen simple substance (I)2,Br2) And the like under the catalytic reaction condition (see US 2010072887A; J.am.chem.Soc,72,5753-5754, 1950; CN 105017302A; european Journal of Organic Chemisty,2017(39), 5892-; Chemistry-A European Journal,25(8),1936-1940, 2019; Chemistry-AEuroplan Journal,24(43), 10971-; ) (3) using biphenyl dihalide (Br, I) compound as raw material, preparing and obtaining diaryl under the condition of selenium dichloride/butyl lithiumSelenophene (CN104125951A), or diarylselenophene prepared by reaction under the condition of copper/alkali/selenium powder (Organic Chemistry Frontiers,5(9), 1488-; (4) the diaryl selenophene compound (CN 106397397A; Organic Letters,18 (21)), 5756-. Although the prior art discloses various synthetic routes represented by the above, these methods are extremely difficult and expensive for obtaining reaction raw materials, use expensive catalytic reaction systems, harsh reaction conditions and complicated operation, and have the disadvantages of poor universality of reaction substrates, low atom economy, low yield of target products and the like, so that the technicians in the field still need to pay large cost in preparing the required dibenzoselenophene compounds. Based on this, it is important to develop a method for synthesizing dibenzoselenophene compounds with high efficiency, environmental protection and simplicity.
Disclosure of Invention
The invention aims to enrich the synthesis way for preparing dibenzoselenophene compounds in the prior art and provide a brand-new synthesis strategy. The method is characterized in that a C-Se bond is formed through the free radical cyclization of a biaryl boric acid substrate catalyzed by TMSCN and selenium powder, so that a dibenzoselenophene compound is constructed. The new strategy has the advantages of no metal participation, no additive promotion, wide substrate range, good functional group compatibility, simple operation, high yield and the like.
The invention provides a method for synthesizing a dibenzoselenophene compound, which comprises the following steps:
sequentially adding a biaryl boric acid substrate shown in the formula a, TMSCN, selenium powder and an organic solvent into a reactor, stirring and reacting the reaction mixture for 4-48 hours at the temperature of 100-150 ℃ in the air atmosphere, cooling to room temperature after the reaction is completed, diluting the reaction mixture with diethyl ether, filtering through a silica gel pad, decompressing and concentrating filtrate, and purifying the residue through silica gel flash chromatography to obtain the dibenzoselenophene compound shown in the formula d.
The reaction formula is as follows:
Figure RE-GDA0002757572450000031
wherein,
Figure RE-GDA0002757572450000032
represents substituted or unsubstituted C6-20An aromatic ring; and wherein the "substituents" in said "substituted or unsubstituted" are selected from halogen, C1-6Alkyl radical, C1-6Alkoxy radical, C1-6A haloalkyl group.
Figure RE-GDA0002757572450000033
Represents substituted or unsubstituted C6-20Aromatic ring, substituted or unsubstituted C2-20A heteroaromatic ring; and wherein the "substituents" in said "substituted or unsubstituted" are selected from halogen, C1-6Alkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C1-6A haloalkyl group.
Preferably, the first and second electrodes are formed of a metal,
Figure RE-GDA0002757572450000034
represents substituted or unsubstituted benzene; and wherein the "substituent" in said "substituted or unsubstituted" is selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, butyl, tert-butyl, methoxy, ethoxy, trifluoromethyl.
Figure RE-GDA0002757572450000035
Represents substituted or unsubstituted benzene, naphthalene, anthracene, indene, phenanthrene or pyrene; substituted or unsubstituted indole, furan, benzofuran, benzothiophene, thiophene, or pyridine; and wherein the "substituent" in said "substituted or unsubstituted" is selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, butyl, tert-butyl, methoxy, methylthio, trifluoromethyl.
Most preferably, the compound of formula a has the structure:
Figure RE-GDA0002757572450000041
according to the synthesis method, the feeding molar ratio of the biaryl boric acid substrate, TMSCN and selenium powder in the formula a is 1 (0.01-0.1) to (1-5); preferably, the feeding molar ratio of the biaryl boric acid substrate, TMSCN and selenium powder in the formula a is 1 (0.01-0.05) to 2-4; most preferably, the feeding molar ratio of the biaryl boric acid substrate, TMSCN and selenium powder in the formula a is 1:0.03: 3.
According to the synthesis method of the present invention, the reaction temperature is preferably 120-140 ℃, and most preferably 140 ℃. The reaction time is preferably 12 to 24 hours, preferably 24 hours.
In the present invention, the organic solvent is DMSO. The inventors found during the course of the experiments that the reaction did not proceed using other organic solvents, such as 1, 4-dioxane, toluene, o-xylene, chlorobenzene or DMF.
The synthesis method of the invention achieves the following beneficial technical effects:
the synthetic method disclosed by the invention is used for forming a C-Se bond through the free radical cyclization of the biaryl boric acid substrate catalyzed by TMSCN and selenium powder so as to construct the dibenzoselenophene compound, and is not reported by the prior art. The new strategy has the advantages of easily available reaction raw materials, no metal participation, no additive promotion, wide substrate range, good functional group compatibility, simple operation, high yield of 98 percent and the like.
Detailed Description
The invention is further described with reference to specific examples.
Examples 1-10 reaction condition optimization examples
The optimal reaction conditions are screened by using [1,1' -biphenyl ] -2-yl boric acid shown in a formula 1a as a template substrate. The reaction formula is as follows:
Figure RE-GDA0002757572450000051
example 1
A25 mL Schlenk tube equipped with a stir bar was charged with [1,1' -biphenyl ] -2-ylboronic acid of formula 1a (0.2mmol), Se (0.6mmol) and DMSO (2mL), and the reaction mixture was stirred at 140 ℃ for 24h under an air atmosphere, and no reaction was detected by TLC and/or GC-MS.
Example 2
A25 mL Schlenk tube equipped with a stir bar was charged with [1,1' -biphenyl ] as shown in formula 1a]-2-ylboronic acid (0.2mmol), TMSCN (1 mol%, i.e. 0.002mmol), Se (3 equivalents, i.e. 0.6mmol) and DMSO (2 ml). The reaction mixture was stirred at 140 ℃ for 24h under an air atmosphere. After cooling, the reaction mixture was diluted with 10mL of diethyl ether, filtered through a pad of silica gel and concentrated under reduced pressure. The residue was then purified by silica gel flash chromatography to give the target product phenoxaselenide/phenothiazineselenium of formula 1d in 40% yield. A white solid;1H NMR(500MHz,CDCl3)δ8.24-8.23(m,2H),8.06-8.04 (m,2H),7.62-7.59(m,2H),7.56-7.53(m,2H)；13C NMR(125MHz,CDCl3)δ 139.6,138.5,127.1,126.3,125.1,123.1。
example 3
TMSCN (3 mol%, namely 0.006mmol), the rest of the reaction conditions and the operation are the same as those of example 2, and the yield of the target product of phenoxaselen/phenothiazinoselen shown in formula 1d is 98%
Example 4
The reaction solvent was replaced by 1, 4-dioxane, the other reaction conditions and operation were the same as in example 3, and no reaction was detected by TLC and/or GC-MS.
Example 5
The alternative reaction solvent was toluene, other reaction conditions and operation were the same as in example 3, and no reaction was detected by TLC and/or GC-MS.
Example 6
The reaction solvent was replaced by m-xylene, the other reaction conditions and operation were the same as in example 3, and no reaction was detected by TLC and/or GC-MS.
Example 7
The solvent was chlorobenzene, other reaction conditions and operation were the same as in example 3, and no reaction was detected by TLC and/or GC-MS.
Example 8
The solvent was DMF, other reaction conditions and operation were the same as in example 3, and no reaction was detected by TLC and/or GC-MS.
Example 9
The replacement reaction temperature was 130 ℃ and the other reaction conditions and operations were the same as those in example 3, except that the yield of the target product, namely, phenoxaselenide/phenothiazineselenium represented by the formula 1d, was 71%
Example 10
The replacement reaction temperature was 120 ℃ and the other reaction conditions and operations were the same as those in example 3, except that the yield of the target product, phenoxaselenide/phenothiazineselenium, shown in formula 1d was 56%
The above reaction conditions were investigated and the results showed that the use of 3 mol% TMSCN was necessary and sufficient to completely convert [1,1' -biphenyl ] -2-ylboronic acid to the product in 98% yield. The desired product is not obtained in the absence of TMSCN. Lowering the temperature appropriately lowers the reaction yield. Interestingly, no product was obtained using other solvents.
Examples 11-29 examples of the development of reaction substrates
After determining the optimal reaction conditions, the inventors next investigated the range of adaptation of arylboronic acid substrates. The target products represented by the formulas 2d to 9d were prepared by using the arylboronic acid compounds represented by the formulas 2a to 9a as raw materials under the optimal reaction conditions of example 3 and examining the universality of the optimal reaction conditions. The results are shown in table 1 below:
table 1:
Figure RE-GDA0002757572450000071
wherein the characterization data for compounds 2d to 9d are as follows:
2d, white solid;1H NMR(500MHz,CDCl3)δ7.96-7.94(m,2H),7.80-7.78 (m,1H),7.51-7.49(m,1H),7.40-7.37(m,1H),7.33-7.30(m,1H),7.13-7.09(m, 1H)；13C NMR(125MHz,CDCl3)δ161.8(d,J＝246.3Hz),140.4(d,J＝8.8Hz), 139.1(d,J＝2.5Hz),137.4,134.7(d,J＝2.5Hz),126.6,126.0,125.1,123.7(d,J＝ 8.8Hz),122.6,113.2(d,J＝22.5Hz),112.6(d,J＝23.8Hz)；19F NMR(470MHz, CDCl3)δ-144.4(s,1F).HRMS(ESI):calculated for C12H8FSe[M+H]+250.9770, found 250.9783。
3d, white solid;1H NMR(500MHz,CDCl3)δ8.04-8.02(m,1H),7.96-7.95(m, 1H),7.83-7.82(m,1H),7.64(s,1H),7.41-7.38(m,1H),7.33-7.30(m,1H), 7.23-7.21(m,1H),2.44(s,3H)；13C NMR(125MHz,CDCl3)δ139.5,139.0,138.4, 137.0,135.9,126.4,126.3,126.2,126.1,124.8,122.6,122.5,21.5.HRMS(ESI): calculated for C13H10SeNa[M+Na]+268.9846,found268.9846。
4d, white solid;1H NMR(500MHz,CDCl3)δ8.04-8.02(m,1H),7.98-7.96 (m,1H),7.84-7.83(m,1H),7.72(s,1H),7.44-7.41(m,1H),7.36-7.32(m,2H), 2.55(s,3H)；13C NMR(125MHz,CDCl3)δ140.2,138.9,138.0,137.7,135.7, 126.6,126.0,124.9,124.1,123.3,122.8,122.6,16.2.GC-MS(EI,70eV): calculated for C13H10SSe 277.9668,found 278.0。
5d, white solid;1H NMR(500MHz,CDCl3)δ8.34(s,1H),8.17-8.15(m,1H), 7.98-7.97(m,1H),7.90-7.89(m,1H),7.61-7.59(m,1H),7.51-7.48(m, 1H),7.45-7.42(m,1H)；13C NMR(125MHz,CDCl3)δ143.3,139.8,138.4,137.3, 127.7,124.6(q,J＝270.0Hz),127.4,126.5,126.1,125.3,123.2,123.0(q,J＝3.8 Hz),119.6(q,J＝3.8Hz)；19F NMR(470MHz,CDCl3)δ-61.7(s,3F)。
6d, white solid;1H NMR(500MHz,CDCl3)δ8.16-8.14(m,1H),8.10-8.09 (m,1H),7.96-7.91(m,3H),7.85-7.83(m,1H),7.58-7.51(m,2H),7.49-7.46(m, 1H),7.40-7.37(m,1H)；13C NMR(125MHz,CDCl3)δ139.5,139.4,139.3,135.6, 132.4,131.4,128.9,126.9,126.4,126.3,126.2,126.1,126.0,125.0,123.1,120.8. HRMS(ESI):calculated for C16H11Se[M+H]+283.0021,found 283.0007。
7d white solid；1H NMR(500MHz,CDCl3)δ8.92-8.90(m,1H),8.72-8.70(m, 1H),8.65-8.64(m,1H),8.55-8.54(m,1H),7.95-7.93(m,1H),7.86-7.84(m,1H), 7.64-7.61(m,1H),7.58-7.46(m,4H),7.35-7.32(m,1H)；13C NMR(125MHz, CDCl3)δ141.5,140.6,139.9,131.0,130.7,130.1,130.0,129.2,127.4,127.3,127.1, 127.0,126.6,126.3,125.6,125.3,125.1,124.1,123.9,123.2.HRMS(ESI): calculated for C20H13Se[M+H]+333.0177,found 333.0187。
8d, white solid;1H NMR(500MHz,CDCl3)δ8.02-8.01(m,1H),7.92-7.91 (m,1H),7.69-7.67(m,1H),7.65-7.63(m,1H),7.49-7.46(m,1H),7.39-7.35(m, 1H),7.35-7.33(m,1H),7.32-7.30(m,1H)；13C NMR(125MHz,CDCl3)δ157.9, 154.4,141.5,127.4,127.3,126.4,125.4,125.2,124.9,123.3,121.4,119.9,115.6, 112.4.HRMS(ESI):calculated for C12H9OSe[M+H]+272.9813,found272.9819。
9d, white solid;1H NMR(500MHz,CDCl3)δ8.09-8.07(m,2H),7.99-7.97 (m,1H),7.67(s,1H),7.64-7.62(m,1H),7.27-7.26(m,1H),2.47(s,3H)；13C NMR (125MHz,CDCl3)δ141.2,140.6,139.0,138.4,134.6,128.2(q,J＝32.5Hz), 127.5,126.7,126.2,125.4,123.2(q,J＝3.8Hz),122.5,121.7(q,J＝3.8Hz),21.6；19F NMR(470MHz,CDCl3)δ-61.6(s,3F).GC-MS(EI,70eV):calculated for C14H9F3Se 313.9822,found 314.0。
the results of the research on the universality of the development of the reaction substrate show that the synthetic strategy is suitable for the reaction substrates of which the ring A is a benzene ring or a substituted benzene ring and the ring B is a benzene ring, a condensed aromatic ring or an aromatic heterocyclic ring and the like with electron donating or electron withdrawing groups and has different structures and/or substituents, and can prepare and obtain corresponding target products with moderate to excellent yield. This shows that the preparation method of the invention has good universality for various aryl boric acid substrates under the optimal process conditions.

Claims (8)

1. A synthetic method of a dibenzoselenophene compound comprises the following steps:
sequentially adding a biaryl boric acid substrate shown in the formula a, TMSCN, selenium powder and an organic solvent into a reactor, stirring and reacting a reaction mixture for 4-48 hours at the temperature of 100-150 ℃ in the air atmosphere, cooling to room temperature after the reaction is completed, diluting the reaction mixture with diethyl ether, filtering through a silica gel pad, decompressing and concentrating filtrate, and purifying residues through silica gel flash chromatography to obtain a dibenzoselenophene compound shown in the formula d;
the reaction formula is as follows:
Figure FDA0002982070930000011
wherein,
Figure FDA0002982070930000012
represents substituted or unsubstituted C6-20An aromatic ring; and wherein the "substituents" in said "substituted or unsubstituted" are selected from halogen, C1-6Alkyl radical, C1-6Alkoxy radical, C1-6A haloalkyl group;
Figure FDA0002982070930000013
represents substituted or unsubstituted C6-20Aromatic ring, substituted or unsubstituted C2-20A heteroaromatic ring; and wherein the "substituents" in said "substituted or unsubstituted" are selected from halogen, C1-6Alkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C1-6A haloalkyl group;
and wherein the organic solvent is DMSO.
2. The method of synthesis according to claim 1,
Figure FDA0002982070930000014
represents substituted or unsubstituted benzene; and wherein said "substituted or unsubstitutedThe "substituent" in (1) is selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, butyl, tert-butyl, methoxy, ethoxy, trifluoromethyl;
Figure FDA0002982070930000021
represents substituted or unsubstituted benzene, naphthalene, anthracene, indene, phenanthrene or pyrene; substituted or unsubstituted indole, furan, benzofuran, benzothiophene, thiophene, or pyridine; and wherein the "substituent" in said "substituted or unsubstituted" is selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, butyl, tert-butyl, methoxy, methylthio, trifluoromethyl.
3. The method of claim 2, wherein the compound of formula a has the structure:
Figure FDA0002982070930000022
4. the synthesis method of claim 1, wherein the molar ratio of the biaryl boronic acid substrate of formula a to TMSCN to selenium powder is 1 (0.01-0.1) to (1-5).
5. The synthesis method of claim 4, wherein the molar ratio of the biaryl boronic acid substrate of formula a to TMSCN to selenium powder is 1 (0.01-0.05) to (2-4).
6. The synthesis method of claim 5, wherein the molar ratio of the biaryl boronic acid substrate of formula a to TMSCN to selenium powder is 1:0.03: 3.
7. The method as claimed in claim 1, wherein the reaction temperature is 120-140 ℃ and the reaction time is 12-24 h.
8. The synthesis process according to claim 7, characterized in that the reaction temperature is 140 ℃ and the reaction time is 24 hours.
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